CN103858935B - A kind of liquid silver-graphene oxide complex compound and preparation method thereof and application - Google Patents
A kind of liquid silver-graphene oxide complex compound and preparation method thereof and application Download PDFInfo
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- CN103858935B CN103858935B CN201410129503.9A CN201410129503A CN103858935B CN 103858935 B CN103858935 B CN 103858935B CN 201410129503 A CN201410129503 A CN 201410129503A CN 103858935 B CN103858935 B CN 103858935B
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Abstract
The invention belongs to anti-biotic material preparation field, particularly a kind of preparation method of graphene oxide/silver/modifying titanium dioxide compound and application.First, take crystalline flake graphite as raw material, adopt Hummer legal system for graphene oxide, and be made into graphene oxide solution, then have the nano titanium oxide of polyacrylate with surface grafting, and silver salt jointly mixes, boils, super filter tube wash-out, obtains composite slow-release anti-biotic material.Above-mentioned anti-biotic material and thermoplastic resin are extruded, blown film, the plastics prepared have the high-efficiency antimicrobial effect of long duration.
Description
Technical field
The invention belongs to anti-biotic material preparation field, particularly a kind of preparation method of graphene oxide/silver/modifying titanium dioxide compound and application.
Background technology
Microbe species is various, comprise prokaryotic micro-organisms (as bacterium), eukaryotic microorganisms (as fungi, algae and protozoon) and acellular biology (as virus) three major types, their individualities are small, but closely bound up with human lives, production, existence, relate generally to the numerous areas such as health, food, medicine, industrial or agricultural, environmental protection.Wherein, the infection of pathogenic microbes especially bacterium brings great harm to aquaculture and human health, causes huge economic loss.Therefore, about the research of antibiosis and practical application are always subject to extensive concern.Traditional antibacterial agent comprises antibiotic and chemosterilant (as free chlorine, chloramines, ozone etc.).Antibiotic has just been widely applied in medical and health industry with its efficient bactericidal effect fast since appearance, in protection human health, played extremely important effect.But due to antibiotic abuse, resistance problem becomes and is on the rise and gives prominence to, as studied the staphylococcus aureus of discovery to benzyl penicillin resistance up to more than 85%.Chemosterilant can realize producing in enormous quantities, but its toxicity problem limits its application in clinical.Based on above problem, work out the efficient anti-biotic material of a kind of new type of safe and there is extremely important practical significance and using value.
In recent years, the develop rapidly of nanoscale science and technology all creates profound influence to every field, and nano material relies on the character of its uniqueness at numerous areas as industry, biomedical sector etc. demonstrate great application prospect.Research finds that some nano materials have good antibacterial activity and not easily produce drug resistance, as gold nano grain, silver nano-grain, Zinc oxide nanoparticle, Cu and its oxides nano particle etc.Wherein, silver is just acknowledged as since ancient times has anti-microbial property, silver nano-grain then demonstrates more desirable antibacterial activity, has good biological safety simultaneously, and therefore silver nano-grain has broad application prospects in fields such as packaging for foodstuff, purification of water quality and health systems.In addition, research finds to grow other nano particles using nano materials such as list/multi-walled carbon nano-tubes, active carbon, Graphenes as substrate and holder, solves dissolubility and the stability problem of nano particle.But in existing anti-biotic material, silver ion easily enters into ionic condition rapidly by chemical bound state, leaves the system of composite, thus lower the anti-microbial property of material.
Summary of the invention
Technical problem to be solved by this invention is: in existing anti-biotic material, and silver ion easily enters into ionic condition rapidly by chemical bound state, leaves the system of composite, thus lowers the anti-microbial property of material.
For solving this technical problem, the invention provides a kind of preparation method with the anti-biotic material of slow release, concrete steps are:
(1) take crystalline flake graphite as raw material, adopt Hummer legal system for graphene oxide, and make the ultrasonic graphene oxide hydrosol obtaining clarifying of graphene oxide suspension that 10mL concentration is 2.5mg/mL, then add KOH solid by final concentration 0.10g/mL and react 2.5 hours under 60 DEG C of water bath, add concentrated hydrochloric acid (Solute mass fraction is 37%) adjustment pH value of solution=1.5 afterwards, as solution A
(2) nano titanium oxide surface-grafted polyacrylic acid ester: take reactant by ratio of quality and the number of copies, first to TiO
2carry out silane treatment, washing, oven dry; By the TiO processed
2put into distilled water to be uniformly dispersed, add sodium hydroxide solution, mechanical agitation is warming up to 70 ~ 80 DEG C simultaneously, pass into nitrogen to remove the air in reactor, start to drip acrylate monomer after adding half initator, drip off in 30 ~ 60min, after reaction 1 ~ 2h, add remaining half initator, then continue reaction 6 ~ 8h; After reaction terminates, vacuum filtration product, washs post-drying with distilled water,
Wherein, ratio of quality and the number of copies is, nano titanium oxide 5 ~ 10 parts; Silane coupler 5 ~ 10 parts; Acrylate monomer 50 parts ~ 100 parts; Initator 0.5 ~ 1.5 part;
(3) surface grafting obtained in step (2) there is the nano titanium oxide of polyacrylate, join in the solution A obtained in step (1) with silver nitrate pressed powder, after mixing, boil 3h in 100 DEG C, super filter tube wash-out three times, obtain composite slow-release anti-biotic material
Wherein, the mass ratio that feeds intake of the silver nitrate pressed powder added and graphene oxide is 1:8-12, and the surface grafting added has the mass ratio that feeds intake of the nano titanium oxide of polyacrylate and graphene oxide to be 0.08:1.
Present invention also offers a kind of above-mentioned slowly released type antibiotic material and prepare the application in antibiotic plastic technique, by ratio of weight and the number of copies: by above-mentioned sustained-release antibacterial material 5 parts, 5 parts, plasticizer, thermoplastic resin 90 parts, after mixing, by twin (double) screw extruder mixing granulator, regulate extruding condition, screw speed 60-150r/min, extruder each section of temperature be set as respectively 90-110 DEG C, 110-130 DEG C, 120-150 DEG C, 130-160 DEG C, 140-180 DEG C, 130-170 DEG C and 130-160 DEG C; Through inflation film manufacturing machine blown film after granulation, blown film temperature is 130-180 DEG C, i.e. the obtained antimicrobial macromolecule material with sustained release performance,
As preferably, sustained-release antibacterial material before being mixed into twin (double) screw extruder, first through airslide disintegrating mill pulverization process,
Wherein, thermoplastic resin is low density polyethylene (LDPE) (LDPE) resin, before being mixed into twin (double) screw extruder, and first dry 8-12h in 70-80 DEG C of environment,
Plasticizer is phthalic acid ester, polyethylene glycol.
Beneficial effect of the present invention is: with lone pair electrons, atom (as nitrogen, oxygen, sulphur etc.), coordination can occur by the unsaturated coordination ability of silver ion, utilize in graphene oxide composite material and can produce chemical constraint effect with silver ion containing carboxyl and amino etc., silver carboxylate and alcohol silver amide complex compound is formed with ionic bond and coordinate bond, silver ion is hindered to enter ionic condition rapidly by chemical bound state, adjustment release speed with limitation, extend release time, reach the high-efficiency antimicrobial effect of long duration.Slowly released type antibiotic material is added in plastics, makes plastics have higher anti-microbial property.
Modified titanium dioxide combines with graphene oxide again, through the TiO of surface grafting
2there is good dispersiveness in graphene oxide, avoid without any surface-treated TiO
2the phenomenon of reuniting is there is in resin matrix; TiO
2ester group in the polyacrylate of surface grafting and the carboxyl in graphene oxide composite material and amino etc., can form hydrogen bond action, improve compatibility, adhesion; The existence of modifying titanium dioxide, can assisted oxidation Graphene, forms constraint effect to silver ion, increases sustained release performance.
Figure of description
Fig. 1: in specific embodiment 1, conventional nano titanium dioxide and surface grafting have the infrared spectrogram of the nano titanium oxide of polyacrylate.
Fig. 2: the flow process of nano titanium oxide surface-grafted polyacrylic acid ester.
Embodiment
Embodiment 1
Take crystalline flake graphite as raw material, adopt Hummer legal system for graphene oxide: first to take 0.5g crystalline flake graphite, 0.25gKNO
3, be placed in 500mL there-necked flask, add the dense H of 12mL
2sO
4, stir 30min at the environment lower magnetic force of ice bath.Then slowly 1.5gKMnO is added
4, stir 24h at 35 DEG C, more slowly instill 150mLH
2o, stirs 12h.Again there-necked flask is moved in oil bath pan, at 98 DEG C, react 24h.To be cooled to filtering and washing after room temperature, first with HCl washing, then use H
2o is washed till neutrality, prepares graphene oxide.
(1) graphene oxide of above-mentioned preparation is utilized, make the ultrasonic graphene oxide hydrosol obtaining clarifying of graphene oxide suspension that 10mL concentration is 2.5mg/mL, then add KOH solid by final concentration 0.10g/mL and react 2.5 hours under 60 DEG C of water bath, add concentrated hydrochloric acid (Solute mass fraction is 37%) adjustment pH value of solution=1.5 afterwards, as solution A
(2) in a kettle., 10 parts of dried nano-TiOs are added successively
2(particle diameter is 1um), the gamma-aminopropyl-triethoxy-silane of the dimethylbenzene of 100 parts and 5 parts, mechanical agitation 8h.After reaction terminates, filter, absolute ethanol washing, vacuum drying.Take 8 parts of nano-TiOs through silane treatment
2be placed in reactor, add the sodium hydroxide solution of the distilled water of 100 parts, 5 parts of 0.5mol/L successively, mechanical agitation is slowly warming up to 70 DEG C, pass into nitrogen to remove the air (time is at about 30min) in reactor, add the ammonium persulfate of 0.25 part, drip the dodecafluoroheptyl methacrylate (dripping off in 30min) of 50 parts slowly, after reaction 2h simultaneously.Add the ammonium persulfate of remaining 0.25 part, continue reaction 8h, after reaction terminates, vacuum filtration product, distilled water washing for several times, is dried,
Fig. 1 is the infrared spectrogram that conventional nano titanium dioxide and surface grafting have the nano titanium oxide of polyacrylate, in figure, two curves are respectively the infrared spectrum of the titanium dioxide of titanium dioxide and graft modification, there is new absworption peak in the titanium dioxide can significantly observed from figure after modification, wherein, 2916.24cm
-1, 2848.73cm
-1for CH
2stretching vibration peak, 1702.63cm
-1for the stretching vibration peak of C=O, 1463.87cm
-1for the flexural vibrations of C-H, but there is skew due to the fluorine having electronegativity strong above the carbon atom that closes on, at 990cm from figure
-1there is more weak absworption peak in place, is the absorption vibration peak of C-F key.Therefore, can to draw from Fig. 1, acrylate copolymer in titanium dioxide surface grafting.
(3) surface grafting obtained in step (2) there is the nano titanium oxide of polyacrylate, join in the solution A obtained in step (1) with silver nitrate pressed powder, after mixing, boil 3h in 100 DEG C, super filter tube wash-out three times, obtain composite slow-release anti-biotic material
Wherein, the mass ratio that feeds intake of the silver nitrate pressed powder added and graphene oxide is 1:8, and the surface grafting added has the mass ratio that feeds intake of the nano titanium oxide of polyacrylate and graphene oxide to be 0.08:1.
By ratio of weight and the number of copies: be 0.910 ~ 0.925 gram/cc by above-mentioned sustained-release antibacterial material 5 parts, plasticizer DOP 5 parts, thermoplastic resin LDPE(density, fusing point is 107 DEG C) 90 parts, sustained-release antibacterial material is before being mixed into twin (double) screw extruder, first through airslide disintegrating mill pulverization process, low density polyethylene (LDPE) (LDPE) resin, before being mixed into twin (double) screw extruder, first dry 10h in 70-80 DEG C of environment
After above-mentioned each raw material blending, by twin (double) screw extruder mixing granulator, regulate extruding condition, screw speed 120r/min, extruder each section of temperature is set as 100 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C and 140 DEG C respectively; Through inflation film manufacturing machine blown film (thickness is 3mm) after granulation, blown film temperature is 130 DEG C, i.e. the obtained antimicrobial macromolecule material with sustained release performance.
Comparative example 1(, compared with embodiment 1, in composite slow-release anti-biotic material, does not add " titanium dioxide that surface grafting has polyacrylate ")
(1) preparation method of graphene oxide as shown in Example 1, make the ultrasonic graphene oxide hydrosol obtaining clarifying of graphene oxide suspension that 10mL concentration is 2.5mg/mL, then add KOH solid by final concentration 0.10g/mL and react 2.5 hours under 60 DEG C of water bath, add concentrated hydrochloric acid (Solute mass fraction is 37%) adjustment pH value of solution=1.5 afterwards, as solution A
(2) in solution A, add silver nitrate pressed powder, boil 3h after mixing in 100 DEG C, super filter tube wash-out three times, obtains composite slow-release anti-biotic material,
Wherein, the mass ratio that feeds intake of the silver nitrate pressed powder added and graphene oxide is 1:8.
Utilize above-mentioned composite slow-release anti-biotic material, preparation has the antimicrobial macromolecule membrane material of sustained release performance, and preparation method as described in Example 1.
Comparative example 2(, compared with embodiment 1, in composite slow-release anti-biotic material, does not add " graphene oxide ")
(1) in a kettle., 10 parts of dried nano-TiOs are added successively
2(particle diameter is 1um), the gamma-aminopropyl-triethoxy-silane of the dimethylbenzene of 100 parts and 5 parts, mechanical agitation 8h.After reaction terminates, filter, absolute ethanol washing, vacuum drying.Take 8 parts of nano-TiOs through silane treatment
2be placed in reactor, add the sodium hydroxide solution of the distilled water of 100 parts, 5 parts of 0.5mol/L successively, mechanical agitation is slowly warming up to 70 DEG C, pass into nitrogen to remove the air (time is at about 30min) in reactor, add the ammonium persulfate of 0.25 part, drip the dodecafluoroheptyl methacrylate (dripping off in 30min) of 50 parts slowly, after reaction 2h simultaneously.Add the ammonium persulfate of remaining 0.25 part, continue reaction 8h, after reaction terminates, vacuum filtration product, distilled water washing for several times, is dried,
(2) surface grafting obtained in step (1) is had the nano titanium oxide of polyacrylate, and silver nitrate pressed powder joins in deionized water, boils 3h after mixing in 100 DEG C, super filter tube wash-out three times, obtains composite slow-release anti-biotic material,
Wherein, the silver nitrate pressed powder added and surface grafting have the mass ratio that feeds intake of the nano titanium oxide of polyacrylate to be 1:0.64.
Utilize above-mentioned composite slow-release anti-biotic material, preparation has the antimicrobial macromolecule membrane material of sustained release performance, and preparation method as described in Example 1.
Be below utilize the membrane material in embodiment 1, comparative example 1, comparative example 2, carry out antibacterial experiment.Respectively by Escherichia coli, salmonella, staphylococcus aureus, on the membrane material in embodiment 1, comparative example 1, comparative example 2, cultivate three days in 37 DEG C, observe bacterial growth situation every day, carry out colony counting; 1-3d represents cultivated days.Concrete outcome is in table 1:
Table 1
In data as can be seen from table 1, by contrast, the antibiotic plastic film of preparation in embodiment 1, to the inhibitory action that bacterium has good inhibition and continues, after three days are cultivated at 37 DEG C to bacterium, still demonstrate the effect that reasonable anti-bacteria is produced;
In comparative example 1, although the incipient stage, antibiotic plastic film inhibits the growth of bacterium well, of long duration, and the antibacterial effect of anti-biotic material just slowly fails.This may be because silver has entered into ionic condition by chemical bound state, thus have left system further, and result in anti-biotic material and gradually fail along with the time.
Below by another experiment, carry out the sustained release performance of composite antibacterial material in dedicated Authentication the present invention:
Respectively by the membrane material in embodiment 1, comparative example 1, comparative example 2, be cut into the test specimen that length and width specification is 100mm × 10mm size, the antimicrobial film material in each embodiment, be cut into 3 samples, count A1, A2, A3(embodiment 1); B1, B2, B3(comparative example 1); C1, C2, C3(comparative example 2),
By each sample, in the test tube placing 10mL distilled water, soak a couple of days (in insulating box 37 DEG C) obtain leaching liquor, A1, B1, C1 soak 1 day; A2, B2, C2 soak 2 days; A3, B3, C3 soak 3 days.
The mensuration of silver ion and titanium ion in leaching liquor:
X-se-ries II type icp ms (U.S.'s match is silent flies generation that science and technology) is adopted to analyze leaching liquor.After in test tube, leaching liquor is with people's atomization system to be atomized by carrier gas (argon), the axial passage of plasma is entered with aerosol form, by fully evaporation, atomization and ionization in high temperature and inert atmosphere, the ion produced enters vacuum system through sampling spiroid and intercepting cone, focusing on through ion mirror, being leaned on than being separated according to matter by quadrupole mass filter.Ion electron multiplier through mass spectrograph counts, and the signal produced is by computer disposal.According to the position of mass spectra peak and the relation of concentration of element and count intensity, carry out the qualitative and quantitative analysis of element in sample, draw the release concentration of silver ion and titanium ion.Concrete data are as shown in table 2.
Table 2: under various sample and different soaking conditions, the concentration (μ g/L) of silver ion and titanium ion in leaching liquor
As can be seen from the data that A1, A2, A3 are corresponding, between modified titanium dioxide and graphene oxide, binding ability is good, and soak 1 day-3 days, in leaching liquor, the concentration of titanium ion is substantially constant; And after soaking 1 day, in leaching liquor, titanium ion is 0.26 μ g/L(A1), here titanium ion is also probably in composite antibacterial material, originally just failed to form chemically combined free titanium with graphene oxide, enter into leaching liquor, although and below soak time increase, almost free shape titanium in composite, therefore, in leaching liquor, titanium ion concentration does not have large increase yet.
Comparing embodiment 1(A1, A2, A3) with comparative example 1(B1, B2, B3) data, can find out, due to the existence of modifying titanium dioxide, can assisted oxidation Graphene, constraint effect is formed to silver ion, increases sustained release performance.
Comparative example 3:(is compared with embodiment 1, and in composite slow-release anti-biotic material, " titanium dioxide " that adds is pure titanium dioxide, and its surface does not have graft polypropylene acid esters)
(1) preparation method of graphene oxide as shown in Example 1, make the ultrasonic graphene oxide hydrosol obtaining clarifying of graphene oxide suspension that 10mL concentration is 2.5mg/mL, then add KOH solid by final concentration 0.10g/mL and react 2.5 hours under 60 DEG C of water bath, add concentrated hydrochloric acid (Solute mass fraction is 37%) adjustment pH value of solution=1.5 afterwards, as solution A
(2) in solution A, add silver nitrate pressed powder and nano titanium dioxide powder, boil 3h after mixing in 100 DEG C, super filter tube wash-out three times, obtains composite slow-release anti-biotic material,
Wherein, the mass ratio that feeds intake of the silver nitrate pressed powder added and graphene oxide is 1:8; The mass ratio that feeds intake of the nano titanium oxide added and graphene oxide is 0.08:1.
Utilize above-mentioned composite slow-release anti-biotic material, preparation has the antimicrobial macromolecule membrane material of sustained release performance, and preparation method as described in Example 1.
By the membrane material in comparative example 3, be cut into the sample that length and width specification is 100mm × 10mm size, totally 3 samples, count D1, D2, D3, by these 3 samples, be positioned over respectively in the test tube of 10mL distilled water and soak a couple of days (in insulating box 37 DEG C) and obtain leaching liquor, D1 soaks 1 day; D2 soaks 2 days; D3 soaks 3 days, and consistent with operation in table 2 to the assay method of silver ion in leaching liquor and titanium ion, concrete data are as shown in table 3.
Table 3: in comparative example 3, each sample under different soaking conditions, in leaching liquor silver ion and titanium ion concentration (
μg/L)
| 1 day | 2 days | 3 days | |
| Sample | D1 | D2 | D3 |
| Silver ion | 3.21 | 12.45 | 18.68 |
| Titanium ion | 0.56 | 0.91 | 1.72 |
Table 3, compared with the data of A1, A2, A3 in table 2, can be found out: between the titanium dioxide of non-modified and graphene oxide, binding ability seems slightly weak, along with the prolongation of soak time, constantly has titanium ion to depart from composite antibacterial material system; And due to the disengaging of titanium ion, the effect that assisted oxidation Graphene fetters silver ion also reduces.
Claims (7)
1. have a preparation method for the anti-biotic material of slow release, it is characterized in that, concrete steps are:
(1) take crystalline flake graphite as raw material, adopt Hummer legal system for graphene oxide, and make the ultrasonic graphene oxide hydrosol obtaining clarifying of graphene oxide suspension that 10mL concentration is 2.5mg/mL, then add KOH solid by final concentration 0.10g/mL and react 2.5 hours under 60 DEG C of water bath, add concentrated hydrochloric acid adjustment pH value of solution=1.5 that Solute mass fraction is 37% afterwards, as solution A;
(2) nano titanium oxide surface-grafted polyacrylic acid ester: take reactant, first to TiO by the ratio of quality and the number of copies of nano titanium oxide 5 ~ 10 parts, silane coupler 5 ~ 10 parts, acrylate monomer 50 ~ 100 parts, initator 0.5 ~ 1.5 part
2carry out silane treatment, washing, oven dry; By the TiO processed
2put into distilled water to be uniformly dispersed, add sodium hydroxide solution, mechanical agitation is warming up to 70 ~ 80 DEG C simultaneously, pass into nitrogen to remove the air in reactor, start to drip acrylate monomer after adding half initator, drip off in 30 ~ 60min, after reaction 1 ~ 2h, add remaining half initator, then continue reaction 6 ~ 8h; After reaction terminates, vacuum filtration product, washs post-drying with distilled water;
(3) nano titanium oxide of polyacrylate and silver nitrate pressed powder is had by the surface grafting obtained in step (2) to join in the solution A obtained in step (1), 3h is boiled in 100 DEG C after mixing, super filter tube wash-out three times, obtains composite slow-release anti-biotic material.
2. have the preparation method of the anti-biotic material of slow release as claimed in claim 1, it is characterized in that: in step (3), the mass ratio that feeds intake controlling silver nitrate pressed powder and graphene oxide is 1:8-12.
3. have the preparation method of the anti-biotic material of slow release as claimed in claim 1, it is characterized in that: in step (3), control surface is grafted with the nano titanium oxide of polyacrylate and the mass ratio that feeds intake of graphene oxide is 0.08:1.
4. the application of the slow release anti-biotic material that the preparation method as described in any one of claims 1 to 3 prepares, is characterized in that: described is applied as the application that slow release anti-biotic material improves thermoplastic antibiotic property, is specially,
By ratio of weight and the number of copies, by described sustained-release antibacterial material 5 parts, 5 parts, plasticizer, thermoplastic resin 90 parts, after mixing, by twin (double) screw extruder mixing granulator, regulate extruding condition, screw speed 60-150r/min, extruder each section of temperature be set as respectively 90-110 DEG C, 110-130 DEG C, 120-150 DEG C, 130-160 DEG C, 140-180 DEG C, 130-170 DEG C and 130-160 DEG C; Through inflation film manufacturing machine blown film after granulation, blown film temperature is 130-180 DEG C, i.e. the obtained antimicrobial macromolecule material with sustained release performance.
5. the application of slow release anti-biotic material as claimed in claim 4, is characterized in that: described sustained-release antibacterial material is before being mixed into twin (double) screw extruder, first through airslide disintegrating mill pulverization process.
6. the application of slow release anti-biotic material as claimed in claim 4, is characterized in that: described thermoplastic resin is ldpe resin, and thermoplastic resin is before being mixed into twin (double) screw extruder, and elder generation is dry 8-12h in 70-80 DEG C of environment.
7. the application of slow release anti-biotic material as claimed in claim 4, is characterized in that: described plasticizer is phthalic acid ester or polyethylene glycol.
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| CN107904960B (en) * | 2017-10-28 | 2020-09-15 | 安徽博朗凯德车用皮革科技有限公司 | Preparation method of smooth artificial synthetic leather |
| CN109580760B (en) * | 2018-10-12 | 2021-05-04 | 浙江工商大学 | Method for detecting hyriopsis cumingii lipid by using modified sharp knife through real-time mass spectrometry |
| CN110093004A (en) * | 2019-05-06 | 2019-08-06 | 辛集市旭远新材料科技有限公司 | A kind of nano-antibacterial ABS plastic and preparation method thereof |
| CN111183979A (en) * | 2020-01-31 | 2020-05-22 | 合肥学院 | High-efficiency composite inorganic antibacterial agent and preparation method thereof |
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